Process for preparation of regioregular poly(3-substituted-thiophene)

ABSTRACT

The invention provides a method of preparing regioregular HT poly(3-substituted-thiophene). The method includes contacting a 3-substituted-thiophene-metal complex with a manganese(II) halide to provide a 3-substituted-thiophene-manganese complex; and contacting the thiophene-manganese complex with a nickel(II) catalyst to provide the regioregular HT poly(3-substituted-thiophene). The substitution at the 3-position can be a variety of different groups. Additionally, unsubstituted and 3,4-disubstituted polythiophenes can also be prepared by the method. Electronic devices can be made using the polymers prepared as described herein.

RELATED APPLICATIONS

This application claims priority under 35 U.S.C. §119(e) to U.S.Application Ser. No. 60/804,139, filed Jun. 7, 2006, which applicationis incorporated herein by reference.

FIELD OF INVENTION

The invention relates to an improved process for making substitutedpolythiophene polymers having high regioselectivity in a more efficientand less costly manner.

BACKGROUND OF THE INVENTION

Polythiophenes have received significant attention recently due to theirnonlinear optical properties, electro-conductivity, and other valuableproperties. They can be employed in electrical components such astransistors, diodes, and triodes in a variety of applications. The useof polythiophenes for these and other applications has often beenhampered by irregular conductivity due a lack of purity.

There are several known synthetic methods for preparing polythiophene.These known techniques, however, often provide substitutedpolythiophenes that have a less than optimal regiospecificity. Highlyregioregular polythiophenes are desired because monomer orientation hasa great influence on the electro-conductivity of the polymer. A highlyregioregular polythiophene allows for improved packing and optimizedmicrostructure, leading to improved charge carrier mobility.

Accordingly, there remains a need for improved synthetic methods forhigh purity and highly regioregular polythiophene polymers. Also neededare devices with high purity regioregular polythiophene polymercomponents for improved ease of manufacture and device operation.

SUMMARY

The invention is directed to a method of preparing a regioregularpolythiophene. The polythiophene can be a 3-substituted polythiophene.The polythiophene can also be a 3,4-disubstituted polythiophene or anunsubstituted polythiophene.

The method of preparing regioregular head-to-tail (“HT”)poly(3-substituted-thiophene) includes contacting a3-substituted-thiophene-metal complex with a manganese(II) halide toprovide a 3-substituted-thiophene-manganese complex; and contacting thethiophene-manganese complex with a nickel (II) catalyst to provide theregioregular HT poly(3-substituted-thiophene). Alternatively, thenickel(II) catalyst and the thiophene-manganese complex may be contactedto provide the regioregular HT poly(3-substituted-thiophene). The3-substituted-thiophene-metal complex can be prepared by a method thatincludes contacting a 2,5-dihalo-3-substituted-thiophene and anorganometallic reagent to provide the 3-substituted-thiophene-metalcomplex. The organometallic reagent can be a Grignard reagent, aGrignard-ate complex, an alkyl lithium reagent, an alkyl lithiumcuprate, an alkyl aluminum reagent, or an organozinc reagent.

The invention is also directed to a conductive polymer composed of animproved regioregular polythiophene having superior electroconductiveproperties. The improved polythiophene is characterized by its monomericcomposition, its degree of regioregularity, and its physical propertiessuch as its molecular weight and number average molecular weight, itspolydispersity, its conductivity, its purity obtained directly from itspreparatory features, as well as other properties. The improvedpolythiophene is characterized as well by the process for itspreparation. In particular, the HT regioregularity of the improvedpolythiophene of the invention can be at least about 85%, preferably atleast about 87%, more preferably at least about 90%, even morepreferably at least about 92%, yet more preferably at least about 95%,further preferably at least about 97%, or most preferably at least about99%.

The invention is as well directed to a thin film of a polythiopheneprepared by the methods described herein. The polythiophene film caninclude a dopant. In another aspect of the invention, the polythiophenefilm can be employed to prepare a radio frequency identification (RFID)tag, a plastic lighting device, or an organic light-emitting diode(OLED), such as in an electronic display.

DEFINITIONS

As used herein, certain terms have the following meanings. All otherterms and phrases used in this specification have their ordinarymeanings as one of skill would understand. Such ordinary meanings may beobtained by reference to technical dictionaries, such as Hawley 'sCondensed Chemical Dictionary 11^(th) Edition, by Sax and Lewis, VanNostrand Reinhold, New York, N.Y., 1987; and The Merck Index, 11^(th)Edition, Merck & Co., Rahway N.J. 1989.

As used herein, the term “and/or” means any one of the items, anycombination of the items, or all of the items with which this term isassociated.

As used herein, the singular forms “a,” “an,” and “the” include pluralreference unless the context clearly dictates otherwise. Thus, forexample, a reference to “a formulation” includes a plurality of suchformulations, so that a formulation of compound X includes formulationsof compound X.

As used herein, the term “about” means a variation of 10 percent of thevalue specified; for example, about 50 percent carries a variation from45 to 55 percent. For integer ranges, the term about can include one ortwo integers greater than and less than a recited integer.

As used herein, the term “alkyl” refers to a branched, unbranched, orcyclic hydrocarbon-having, for example, from 1 to 30 carbon atoms, andoften 1 to 12 carbon atoms. Examples include, but are not limited to,methyl, ethyl, 1-propyl (n-propyl), 2-propyl i-propyl), 1-butyl(n-butyl), 2-methyl-1-propyl (i-butyl), 2-butyl (sec-butyl),2-methyl-2-propyl (t-butyl), 1-pentyl (n-pentyl), 2-pentyl, 3-pentyl,2-methyl-2-butyl, 3-methyl-2-butyl, 3-methyl-1-butyl, 2-methyl-1-butyl,1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl,4-methyl-2-pentyl, 3-methyl-3-pentyl, 2-methyl-3-pentyl,2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, hexyl, octyl, decyl,dodecyl, and the like. The alkyl can be unsubstituted or substituted.The alkyl can also be optionally partially or fully unsaturated. Assuch, the recitation of an alkyl group includes both alkenyl and alkynylgroups. The alkyl can be a monovalent hydrocarbon radical, as describedand exemplified above, or it can be a divalent hydrocarbon radical(i.e., alkylene).

As used herein, the term “alkylthio” refers to the group alkyl-S—, wherealkyl is as defined herein. In one embodiment, alkylthio groups include,e.g., methylthio, ethylthio, n-propylthio, iso-propylthio, n-butylthio,tert-butylthio, sec-butylthio, n-pentylthio, n-hexylthio,1,2-dimethylbutylthio, and the like. The alkyl group of the alkylthiocan be unsubstituted or substituted.

As used herein, the term “alkylsilyl” refers to the group alkyl-SiH₂— oralkyl-SiR₂—, where alkyl is as defined herein, and each R isindependently H or alkyl. Thiophenes can be substituted by alkylsilylgroups by any of the many techniques known to those of skill in the art,typically by coupling the thiophene with an alkylsilyl halide, many ofwhich are disclosed in the Aldrich Handbook of Fine Chemicals,2007-2008, Milwaukee, Wis.

As used herein, the term “alkoxy” refers to the group alkyl-O—, wherealkyl is as defined herein. In one embodiment, alkoxy groups include,e.g., methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert-butoxy,sec-butoxy, n-pentoxy, n-hexoxy, 1,2-dimethylbutoxy, and the like. Thealkyl group of the alkoxy can be unsubstituted or substituted.

As used herein, the term “aryl” refers to an aromatic hydrocarbon groupderived from the removal of one hydrogen atom from a single carbon atomof a parent aromatic ring system. The radical can be at a saturated orunsaturated carbon atom of the parent ring system. The aryl group canhave from 6 to 18 carbon atoms. The aryl group can have a single ring(e.g., phenyl) or multiple condensed (fused) rings, wherein at least onering is aromatic (e.g., naphthyl, dihydrophenanthrenyl, fluorenyl, oranthryl). Typical aryl groups include, but are not limited to, radicalsderived from benzene, naphthalene, anthracene, biphenyl, and the like.The aryl can be unsubstituted or optionally substituted, as describedabove for alkyl groups.

As used herein, the terms “film” or “thin film” refers to aself-supporting or free-standing film that shows mechanical stabilityand flexibility, as well as a coating or layer on a supporting substrateor between two substrates.

As used herein, the term “Grignard-ate complex” refers to the complexingor three-dimensional association of one or more Grignard reagents withan alkali salt to form to form the three-dimensional ate complex.

As used herein, the terms “halo” and “halogen” refer to a fluoro,chloro, bromo, or iodo group, substituent, or radical.

As used herein, the term “high purity” refers to a compound or polymerthat is at least about 85%, preferably at least about 87%, morepreferably at least about 90%, even more preferably at least about 92%,yet more preferably at least about 95%, further preferably at leastabout 97%, or most preferably at least about 99% pure. The purity can bedetermined in a wt. %/wt. % manner.

As used herein, the term “heteroaryl” is defined herein as a monocyclic,bicyclic, or tricyclic ring system containing one, two, or threearomatic rings and containing at least one nitrogen, oxygen, or sulfuratom in an aromatic ring, and which can be unsubstituted or substituted,for example, with one or more, and in particular one to three,substituents, as described above in the definition of “substituted.”Examples of heteroaryl groups include, but are not limited to,2H-pyrrolyl, 3H-indolyl, 4H-quinolizinyl, acridinyl, benzo[b]thienyl,benzothiazolyl, β-carbolinyl, carbazolyl, chromenyl, cinnolinyl,dibenzo[b,d]furanyl, furazanyl, furyl, imidazolyl, imidizolyl,indazolyl, indolisinyl, indolyl, isobenzofuranyl, isoindolyl,isoquinolyl, isothiazolyl, isoxazolyl, naphthyridinyl, oxazolyl,perimidinyl, phenanthridinyl, phenanthrolinyl, phenarsazinyl,phenazinyl, phenothiazinyl, phenoxathiinyl, phenoxazinyl, phthalazinyl,pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolyl, pyridazinyl,pyridyl, pyrimidinyl, pyrimidinyl, pyrrolyl, quinazolinyl, quinolyl,quinoxalinyl, thiadiazolyl, thianthrenyl, thiazolyl, thienyl, triazolyl,tetrazolyl, and xanthenyl. In one embodiment the term “heteroaryl”denotes a monocyclic aromatic ring containing five or six ring atomscontaining carbon and 1, 2, 3, or 4 heteroatoms independently selectedfrom non-peroxide oxygen, sulfur, and N(Z) wherein Z is absent or is H,O, alkyl, aryl, or (C₁-C₆)alkylaryl. In another embodiment heteroaryldenotes an ortho-fused bicyclic heterocycle of about eight to ten ringatoms derived therefrom, particularly a benz-derivative or one derivedby fusing a propylene, trimethylene, or tetramethylene diradicalthereto.

As used herein, the terms “heterocycle” or “heterocyclyl” refer to asaturated or partially unsaturated ring system, containing at least oneheteroatom selected from the group oxygen, nitrogen, and sulfur, andoptionally substituted with one or more groups as defined herein underthe term “substituted.” A heterocycle can be a monocyclic, bicyclic, ortricyclic group containing one or more heteroatoms. A heterocycle groupalso can contain an oxo group (═O) attached to the ring. Non-limitingexamples of heterocycle groups include 1,3-dihydrobenzofuran,1,3-dioxolane, 1,4-dioxane, 1,4-dithiane, 2H-pyran, 2-pyrazoline,4H-pyran, chromanyl, imidazolidinyl, imidazolinyl, indolinyl,isochromanyl, isoindolinyl, morpholine, piperazinyl, piperidine,piperidyl, pyrazolidine, pyrazolidinyl, pyrazolinyl, pyrrolidine,pyrroline, quinuclidine, and thiomorpholine. The term “heterocycle” alsoincludes, by way of example and not limitation, a monoradical of theheterocycles described in Paquette, Leo A.; Principles of ModernHeterocyclic Chemistry (W. A. Benjamin, New York, 1968), particularlyChapters 1, 3, 4, 6, 7, and 9; The Chemistry of Heterocyclic Compounds,A Series of Monographs” (John Wiley & Sons, New York, 1950 to present),in particular Volumes 13, 14, 16, 19, and 28; and J. Am. Chem. Soc.1960, 82, 5566. In one embodiment of the invention “heterocycle”includes a “carbocycle” as defined herein, wherein one or more (e.g. 1,2, 3, or 4) carbon atoms have been replaced with a heteroatom (e.g. O,N, or S).

As used herein, the term “HT poly(3-substituted-thiophene)” refers tothe head-to-tail orientation of monomers in apoly(3-substituted-thiophene). The percent regioregularity present in anHT poly(3-substituted-thiophene) can be determined by standard ¹H NMRtechniques. The percent regioregularity can be increased by varioustechniques, including Soxhlet extraction, precipitation, andrecrystallization.

As used herein, the term “regioregular” refers to a polymer where themonomers are arranged in a substantially head-to-tail orientation. Forfurther description and discussion of the terms regiorandom andregioregular (or regioselective), see U.S. Pat. No. 5,756,653, thedisclosure of which is incorporated by reference herein.

As used herein, the term “room temperature” refers to about 23° C.

As used herein, the term “substituted” is intended to indicate that oneor more (e.g., 1, 2, 3, 4, or 5; in some embodiments 1, 2, or 3; and inother embodiments 1 or 2) hydrogen atoms on the group indicated in theexpression using “substituted” is replaced with a selection from theindicated organic or inorganic group(s), or with a suitable organic orinorganic group known to those of skill in the art, provided that theindicated atom's normal valency is not exceeded, and that thesubstitution results in a stable compound. Suitable indicated organic orinorganic groups include, e.g., alkyl, alkenyl, alkynyl, alkoxy, halo,haloalkyl, hydroxy, hydroxyalkyl, aryl, heteroaryl, heterocyclyl,cycloalkyl, alkanoyl, alkoxycarbonyl, amino, alkylamino, dialkylamino,trifluoromethylthio, difluoromethyl, acylamino, nitro, trifluoromethyl,trifluoromethoxy, carboxy, carboxyalkyl, keto, thioxo, alkylthio,alkylsulfinyl, alkylsulfonyl, alkylsilyl, and cyano. Additionally, thesuitable indicated groups can include, e.g., —X, —R, —O⁻, —OR, —SR, —S⁻,—NR₂, —NR₃, ═NR, —CX₃, —CN, —OCN, —SCN, —N═C═O, —NCS, —NO, —NO₂, ═N₂,—N₃, NC(═O)R, —C(═O)R, —C(═O)NRR —S(═O)₂O⁻, —S(═O)₂OH, —S(═O)₂R,—OS(═O)₂OR, —S(═O)₂NR, —S(═O)R, —OP(═O)O₂RR —P(═O)O₂RR, —P(═O)(O⁻)₂,—P(═O)(OH)₂, —C(═O)R, —C(═O)X, —C(S)R, —C(O)OR, —C(O)O⁻, —C(S)OR,—C(O)SR, —C(S)SR, —C(O)NRR, —C(S)NRR, or —C(NR)NRR, where each X isindependently a halogen (or “halo” group): F, Cl, Br, or 1; and each Ris independently H, alkyl, aryl, heterocyclyl, a protecting group, or aprodrug moiety. As would be readily understood by one skilled in theart, when a substituent is keto (i.e., ═O) or thioxo (i.e., ═S), or thelike, then two hydrogen atoms on the substituted atom are replaced.

As used herein, the terms “stable compound” and “stable structure” aremeant to indicate a compound or polymer that is sufficiently robust tosurvive isolation to a useful degree of purity from a reaction mixture.The compounds and polymers of the present invention are typically stablecompounds. Intermediates and metal complexes can be somewhat instable ornon-isolable components of the methods of the invention.

As used herein, the term “thiophene-metal complex” refers to a thiophenemoiety that is associated with a metal. The association can be acovalent bond or the association can have both covalent and ionicbonding character. The complex can be an “ate-complex,” wherein morethan one metal atom and/or more than one thiophene moiety is associatedwith each other.

As used herein, the term “thiophene-manganese complex” refers to athiophene moiety that is associated with a manganese atom. Thethiophene-manganese complex is typically a thiophene-manganese halidecomplex. The halide, or “halo” group can be fluoro, chloro, bromo, oriodo.

As to any of the above groups, which contain one or more substituents,it is understood, of course, that such groups do not contain anysubstitution or substitution patterns that are sterically impracticaland/or synthetically non-feasible. In addition, the compounds of thisinvention include all stereochemical isomers arising from thesubstitution of these compounds.

DETAILED DESCRIPTION OF THE INVENTION General Preparatory Methods

A number of exemplary methods for the preparation of polymers of theinvention are provided herein. These methods are intended to illustratethe nature of such preparations and are not intended to limit the scopeof applicable methods. Certain compounds can be used as intermediatesfor the preparation of other compounds or polymers of the invention.

A general scheme for preparing polythiophenes is provided below.

wherein X is a halogen, R¹ is an alkyl, alkylthio, alkylsilyl, or alkoxygroup that is optionally substituted with one to about five ester,ketone, nitrile, amino, halo, aryl, heteroaryl, or heterocyclyl groups,and the alkyl chain of the alkyl group is optionally interrupted by oneto about ten O, S, and/or NP groups wherein P is a substituent asdescribed above or a nitrogen protecting group; R²—M is anorganometallic reagent that can react with the thiophene to form athiophene metal complex that undergoes transmetallation when introducedto a manganese(II) salt, such as MnF₂, MnCl₂, MnBr₂, or MnI₂; and theNi(II) catalyst is any nickel(II) catalyst that effectuatespolymerization of the thiophene manganese complex.

The invention relates to the transmetallation of a thiophene-metalcomplex with manganese salts to provide a thiophene-manganese complexthat undergoes facile polymerization with a Ni(II) catalyst. Thethiophene-metal complex is typically substituted by a metal at the 2- or5-position, for example, by the exchange of the metal for a halogen thatwas positioned at the 2- or 5-position. The thiophene-metal complex canthen be converted to a thiophene-manganese complex by transmetallation.Thereafter, the thiophene-manganese complex can be readily polymerizedby a Ni(II) catalyst to provide a highly regioregular 3-substitutedpolythiophene. Although it is not intended to be a limitation of theinvention, it is believed that transmetallation to provide thethiophene-manganese complex reduces the activation energy or energeticbarrier for polymerizing the thiophene-based monomer. The use of athiophene-manganese complex thus is believed to provide a more energeticpolymerization that does not require additional heating, and theresulting polymer has a higher regioregularity than does a polymerproduced by heretofore known methods.

In particular, for example, a 2,5-dihalo-3-substituted-thiophene can bedissolved in a suitable solvent, such as an ethereal solvent, forexample, tetrahydrofuran. The reaction flask can be cooled beforeintroduction of the organometallic reagent. The organometallic reagentcan be added into the reaction flask and stirred for a sufficient periodof time to form the thiophene-metal complex by exchanging a group on theorganometallic complex with one of the X (halo) groups of the thiophene.After the thiophene-metal complex has formed, a manganese halide can beadded to the reaction mixture, optionally allowing the reaction to warmto ambient temperature, to afford a transmetallated species.

After transmetallation, the reaction can be allowed to settle and thesolution of the reaction vessel can be transferred to a flask containinga nickel(II) catalyst, optionally dissolved in an ethereal solvent.Alternatively after transmetallation, the flask containing thenickel(II) catalyst may be added to the reaction vessel containing thetransmetallated species. The resulting mixture can be stirred for asufficient amount of time to effect the formation of the polythiophene,which typically precipitates from the reaction mixture. Thepolythiophene can be isolated by transferring the reaction mixture intoa volume of solvent in which the polythiophene is substantiallyinsoluble. Further work-up can include filtering, washing with methanol,and drying under high vacuum. Additional purification can be carried outby Soxhlet extraction with, for example, a hydrocarbon solvent, such ashexanes.

The formation of the polythiophene can be carried out at any suitableand effective temperature. In one embodiment, the polymerization iscarried out at temperatures of about −100° C. to about 150° C. Inanother embodiment, the polymerization is conducted at temperatures ofabout −20° C. to about 100° C. The polymerization can be carried out inthe same solvent as was the preparation of the thiophene metal complex.The polymerization reaction step with the Ni(II) catalyst can be carriedout at about 0° C. to about the boiling point of the solvent used inthis step of the reaction. Typically, the thiophene-manganese complex iscontacted with the nickel(II) catalyst at about −80° C. to about 35° C.,or preferably at about −10° C. to about 30° C., or more preferably atabout 0° C. to about 27° C.

One advantage of the methods described herein for preparingpolythiophenes, however, is that transmetallation of the thiophene-metalcomplex with manganese allows for polymerization at a lower temperaturethan many known methods, such as those described in U.S. Pat. No.6,166,172. Polymerization of the thiophene-manganese complex proceedssmoothly at ambient temperatures (e.g., about 18° C. to about 25° C.)without the need for a heat source or for refluxing conditions. A moresignificant advantage is that the method described herein produces apolymer of greater regioregularity (higher percentage of head-to tailthiophene linkages) than the method described in U.S. Pat. No.6,166,172. Additionally, lower catalyst loading is needed, thusproviding a less expensive procedure.

A variety of organometallic reagents can be used to form thethiophene-metal complex. Suitable organometallic reagents includeGrignard reagents, Grignard-ate complexes, alkyl lithium reagents, alkyllithium cuprates, alkyl aluminum reagents, and organozinc reagents (see,e.g., PCT Patent Application Publication No. WO 2007/011945, which isincorporated herein by reference). Commercial reagents, such asGrignard, Grignard-ate complexes, alkyl lithium, alkyl lithium cuprate,alkyl aluminum, and organozinc reagents can be employed, such as thosedisclosed in the Aldrich Handbook of Fine Chemicals, 2007-2008,Milwaukee, Wis. Any suitable amount of the organometallic reagent can beused. Typically, one to about five equivalents of the organometallicreagent can be employed, based on the amount of the thiophene startingmaterial. The entire reaction sequence can be carried out without anyisolation of intermediates.

The dihalo-thiophenes are typically difluoro-, dichloro-, dibromo-, ordiiodo-thiophenes, but mixed 2,5-dihalosubstituted thiophenes can alsobe employed.

The solvent employed in the methods of the invention can be aproticsolvents. Suitable solvents include ethereal or polyethereal solvents.Examples of such solvents include ethyl ether, methyl-t-butyl ether,tetrahydrofuran (THF), dioxane, diglyme, triglyme, 1,2-dimethoxyethane(DME or glyme), and the like. A typical solvent is tetrahydrofuran.

Catalysts

The catalyst employed in the method of the invention is a Ni(II)catalyst. An effective amount of the Ni(II) catalyst is employed, suchthat a sufficient amount of catalyst is employed to effect the reactionin less than about 5 days. Typically, this is an amount of about 0.01-10mole percent (mol %), however, any amount of the Nickel(II) catalyst canbe employed, such as 50 mol %, 100 mol %, or more. Typically, about 0.1mol % Nickel(II) catalyst to about 5 mol % Nickel(II) catalyst isemployed, or preferably, about 0.1 mol % Nickel(II) catalyst to about 3mol % Nickel(II) catalyst is employed, based on the amount of thiophenemonomer present.

Examples of suitable nickel(II) catalysts include, for example,Ni(PR₃)₂X₂ wherein R is (C₁-C₂₀)alkyl, (C₆-C₂₀)aryl, and X is halo;NiLX₂ wherein L is a suitable nickel(II) ligand and X is halo. Suitablenickel(II) ligands include 1,2-bis(diphenylphosphino)ethane,1,3-diphenylphosphinopropane,[2,2-dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene)] diphenylphosphine,bis(triphenylphosphine), and (2,2′-dipyridine) ligands. Other suitableNi(II) catalysts include Ni(CN)₄ ⁻²; NiO; Ni(CN)₅ ⁻³; Ni₂Cl₈ ⁻⁴; NiF₂;NiCl₂; NiBr₂; NiI₂; NiAs; Ni(dmph)₂ wherein dmph is dimethylglyoximate;BaNiS; [NiX(QAS)]⁺ wherein X is halo and QAS is As(o-C₆H₄AsPh₂)₃;[NiP(CH₂CH₂CH₂AsMe₂)₃CN]⁺; [Ni(NCS)₆]⁻⁴; KNiX₃ wherein X is halo;[Ni(NH₃)₆]⁺²; and [Ni(bipy)₃]+² wherein bipy is bipyridine.

Typical nickel catalysts also include 1,2-bis(diphenylphosphino)ethanenickel(II) chloride (Ni(dppe)Cl₂); 1,3-diphenylphosphinopropanenickel(II) chloride (Ni(dppp)Cl₂); 1,5-cyclooctadiene bis(triphenyl)nickel; dibromo bis(triphenylphosphine) nickel; dichoro(2,2′-dipyridine)nickel; and tetrakis(triphenylphosophine) nickel(0).

General techniques and methods known by those of ordinary skill in theart can be used in methods of the invention, such as the variousstandard procedures for carrying out the polymerization, and forisolating and purifying the products.

Polymer Structure and Properties

The improved polythiophenes of the invention prepared by the methodsdisclosed herein can be unsubstituted, 3-substituted, or3,4-disubstituted thiophenes. These substituents can be any of thegroups recited under the definition of substituents above. In oneembodiment, the thiophene is a 3-substituted thiophene, wherein thesubstituent is an alkyl, alkylthio, alkylsilyl, or alkoxy group. Thesubstituent can be optionally substituted with other functional groups,for example, and with out limitation, one to about five esters, ketones,nitriles, amines, halogens, aryl groups, heterocyclyl groups, andheteroaryl groups. The alkyl chain of the alkyl, alkylthio, alkylsilyl,or alkoxy group can also be interrupted by one or more heteroatoms, suchas O, S, NP groups (wherein P is a substituent or a nitrogen protectinggroup), or combinations thereof.

It is often preferable to include substituents that improve thesolubility of the polythiophene. Such substituents can preferablyinclude groups that include at least about five or six carbon atoms,such as hexyl, hexoxy, hexylthio, and hexylsilyl groups. In anotheraspect of the invention, it can be preferable that the substituentdirectly attached to the 3-position is a heteroatom, such as a sulfur,silicon, oxygen, or nitrogen atom. The heteroatoms can be substitutedwith other appropriate groups, such as are described above in thedefinition of substituted. Heteroatoms at the 3-position of thethiophenes can further enhance the conductivity of the polythiophene by,for example, allowing for delocalization of the aromatic electrons ofthe thiophene ring systems and/or allowing for improved packing andoptimized microstructure of the polymer, leading to improved chargecarrier mobility. In a further aspect of the invention, it can bepreferable to separate an aryl, heteroaryl, or heterocyclyl substituentfrom the thiophene ring by one or more (e.g., one to ten, one to five,or one to three) methylene groups, optionally interrupted by one or moreheteroatoms (e.g., a polyethylene or polyethyleneimine group wherein thegroup includes about 2 to about 10 repeating units. Substituents at the3-position of the thiophene monomer can improve the regioregularity ofthe product polythiophene by providing steric bulk that influences theregiochemistry of the polymerization.

The terminal groups (group at the 2- or 5-position of the terminalthiophene of the polymer) on the product polythiophene can be a hydrogenor a halogen. The terminal group of the polythiophene can also be analkyl or functionalized alkyl group, which can be provided for byquenching the polymerization with an organometallic species, such as anorgano-zinc reagent.

The average weight molecular weight of the polythiophenes prepared bythe methods described herein can be about 5,000 to about 200,000,preferably about 20,000 to about 80,000, and more preferably about40,000 to about 60,000, as determined by GPC using a polystyrenestandard in tetrahydrofuran. The polydispersity index (PDI) can be about1 to about 2.5, or preferably about 1.1 to about 2.4, or more preferablyabout 1.2 to about 2.2.

The regioregularity of the polymers prepared by the methods of theinvention are typically at least about 87% without any purificationafter work-up. It was surprisingly discovered that by employing 1.2equivalents of a manganese halide salt, a higher percent ofregioregularity can be obtained. For example, by employing 1.2equivalents of MnCl₂, based on the amount of 3-substituted thiophenestarting material, an HT polythiophene of at least about 92%regioregularity was obtained. Simple purification techniques, such asSoxhlet extraction with hexanes can improve the regioregularity togreater than about 94%, preferably greater than about 95%, morepreferably greater than about 97%, yet more preferably greater thanabout 98%, or even more preferably greater than about 99%.

The crude polythiophene can be isolated after polymerization byprecipitation in methanol followed by simple filtration of theprecipitated polymer. The crude polymer has superior properties relativeto the crude products of the art. The crude polythiophene of theinvention has higher regioregularity that the known preparatory methods,which reduces the amount of purification necessary to provide a usablematerial for electronic applications.

Higher regioregularity results in higher conductivity of thepolythiophenes. When doped, a regioregular 3-substituted polythiophenecan have a conductivity of about 1,000 seimens/cm, +/−about 400seimens/cm. Regiorandom 3-substituted polythiophenes are typicallyconduct at only about 5-10 seimens/cm. Furthermore, undoped regioregular3-substituted polythiophenes conduct at about 10⁻⁵ to about 10⁻⁶seimens/cm (the semiconductor range), and undoped regiorandompolythiophenes conduct at about 10⁻⁹ seimens/cm.

Polythiophenes can be oxidatively or reductively doped. Dopants that canbe included in the polythiophene polymer matrix include typical dopantsused with conductive organic polymers, including iodine (I₂), bromine(Br₂), ferric chloride, and various arsenate or antimony salts. Otherdopants include various known onium salts, iodonium salts, borate salts,tosylate salts, triflate salts and sulfonyloxyimides. The polythiophenesof the invention can be doped by dissolving the polymer in a suitableorganic solvent and adding the dopant to the solution, followed byevaporation of the solvent. Many variations of this technique can beemployed and such techniques are well known to those of skill in theart. See for example, U.S. Pat. No. 5,198,153.

The polymers of the invention can also include one or more othersuitable components such as, for example, sensitizers, stabilizers,inhibitors, chain-transfer agents, co-reacting monomers or oligimers,surface active compounds, lubricating agents, wetting agents, dispersingagents, hydrophobing agents, adhesive agents, flow improvers, diluents,colorants, dyes, pigments, or dopants. These optional components can beadded to a polymer composition by dissolving the polythiophene in asuitable organic solvent and adding the component to the solution,followed by evaporation of the solvent. In certain embodiments of theinvention, the polythiophene polymers are significantly useful assubstantially pure polymers or as a doped polymers.

Thin Films

The high purity polymers prepared by the methods described herein can beused to form thin films. The thin films can be formed using standardmethods known to those of skill in the art, such as spin coating,casting, dipping, bar coating, roll coating, and the like, using asolution of a polythiophene of the invention dissolved in a solvent. Seefor example, U.S. Pat. Nos. 5,892,244; 6,337,102; 7,049,631; 7,037,767;7,025,277; 7,053,401; and 7,057,339 for methods of preparing thin filmsand organic field effect transistors. The thin films can have a widerange of thickness. A typical thin film is in the range of about 1 μm toabout 1 mm. The thin film can include a coloring agent, a plasticizer,or a dopant. The polythiophenes of the invention can be electricallyconductive, particularly when a dopant is included in the polymermatrix.

Applications of the Regioregular Polythiophenes

The regioregular polythiophenes can be employed in the manufacture oforganic light-emitting diodes (OLEDs). The OLEDs can be used inelectronic displays. The regioregular polythiophenes can also be used toprepare radio frequency identification (RFID) tags. Regioregularpoly(3-alkylthio-thiophenes) are especially useful for preparing thinfilms and organic field effect transistors (OFETs). The polythiophenescan further be used in, for example, optical, electrooptical, electric,electronic, charge transport, electroluminescent, or photoconductormaterials, applications, and devices. Other applications includephotovoltaic devices and plastic lighting. Further applications includetheir use in liquid crystal and/or semiconducting materials, devices, orapplications. The increased conductance of these polymers compared toconventional syntheses allows for improved conductance, and therefore,improved function of these applications and devices.

The invention further relates to the polymers described herein inelectrooptical displays, OLCDs, ELCDs, optical films, reflective films,electronic devices such as OFETs as components of integrated circuits,thin film transistors in flat or flexible panel display applications orfor RFID tags, semiconducting or light-emitting components of organiclight emitting diodes (OLED) applications, electroluminescent displaysor backlights of LCDs, electrode materials in batteries, and the like.

The regioregular polythiophenes are particularly useful for use inplastic electronics, such as for preparing plastic RFID tags, plasticphotovoltaic devices, plastic lighting devices, and OLEDs. Accordingly,the invention provides an electronic device comprising a circuitconstructed with a polymer as described herein, such as a polymerprepared as described in any one of Examples 1-40.

It is to be understood that certain descriptions of the presentinvention have been simplified to illustrate only those elements andlimitations that are relevant to a clear understanding of the presentinvention, while eliminating, for purposes of clarity, other elements.Those of ordinary skill in the art, upon considering the presentdescription of the invention, will recognize that other elements and/orlimitations may be desirable in order to implement the presentinvention. However, because such other elements and/or limitations maybe readily ascertained by one of ordinary skill upon considering thepresent description of the invention, and are not necessary for acomplete understanding of the present invention, a discussion of suchelements and limitations is not provided herein. For example, asdiscussed herein, the materials of the present invention may beincorporated, for example, in electronic devices that are understood bythose of ordinary skill in the art, and, accordingly, are not describedin detail herein.

Furthermore, compositions of the present invention may be generallydescribed and embodied in forms and applied to end uses that are notspecifically and expressly described herein. For example, one skilled inthe art will appreciate that the present invention may be incorporatedinto electronic devices other than those specifically identified herein.

EXAMPLES

The following Examples are illustrative of the above invention. Oneskilled in the art will readily recognize that the techniques andreagents described in the Examples suggest many other ways in which thepresent invention could be practiced. It should be understood that manyvariations and modifications may be made while remaining within thescope of the invention.

Other than in the operating examples, or unless otherwise expresslyspecified, all of the numerical ranges, amounts, values and percentagessuch as those for amounts of materials, times and temperatures ofreaction, ratios of amounts, and others in the following portion of thespecification may be read as if prefaced by the word “about” even thoughthe term “about” may not expressly appear with the value, amount, orrange. Accordingly, unless indicated to the contrary, the numericalparameters set forth in the following specification and attached claimsare approximations that may vary depending upon the desired propertiessought to be obtained by the present invention. At the very least, andnot as an attempt to limit the application of the doctrine ofequivalents to the scope of the claims, each numerical parameter shouldat least be construed in light of the number of reported significantdigits and by applying ordinary rounding techniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contains certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements. Furthermore, when numerical ranges ofvarying scope are set forth herein, it is contemplated that anycombination of these values inclusive of the recited values may be used.

Reactions were typically carried out on a dual manifold vacuum/argon ornitrogen system. The handling of air-sensitive materials was performedunder argon or nitrogen in a dry box when necessary. Chemical reagentswere primarily purchased from Aldrich Chemical Co., Inc.(Milwaukee,Wis.), and were used as received unless indicated otherwise.

Example 1 Preparation of Regioregular HT Poly(3-hexylthiophene) from2,5-Dibromo-3-hexylthiophene and alkyl Grignard in the presence ofManganese Chloride

A 250 mL of round-bottom-flask was charged with2,5-dibromo-3-hexylthiophene (8.15 grams (g), 25 mmol) and 50 mL oftetrahydrofuran. The reaction flask was cooled in an ice-bath. Withstirring at 0° C., cyclohexylmagnesium chloride (2.0 M in ether, 12.5mL, 25 mmol) was slowly added into the reaction flask. After beingstirred at 0° C. for 10 minutes, manganese chloride (0.5 M intetrahydrofuran, 50 mL, 25 mmol) was added to the reaction mixture,which was allowed to warm to room temperature over 20 minutes. Stirringwas discontinued and solids settled to the bottom of the reactionvessel. Without transferring the solids, the reaction solution wascannulated to a flask containing Ni(dppe)Cl₂ (0.04 g, 0.3 mol %) in 10mL of tetrahydrofuran at room temperature. The resulting mixture wasstirred at room temperature for 24 hours. A dark-purple precipitategradually formed over the course of the 24 hours. The entire mixture wasthen poured into 100 mL of methanol. The resulting dark precipitate wasfiltered, washed with methanol, and then dried under high vacuum.

The regioregularity of the polythiophene obtained was about 87%, asdetermined by ¹H NMR analysis.

The average weight molecular weight of the regioregular HTpoly(3-substituted-thiophene) was about 40,000 to about 60,000 asdetermined by GPC using a polystyrene standard in tetrahydrofuran.Light-scatting analysis indicates the average weight molecular weight ismuch higher, in the range of about 80,000 to about 120,000.

Example 2 Preparation of Regioregular HT Poly(3-hexylthiophene) from2,5-Dibromo-3-hexylthiophene and alkyl Grignard in the presence ofManganese Chloride

A 250 mL of round-bottom-flask was charged with2,5-dibromo-3-hexylthiophene (8.15 g, 25 mmol) and 50 mL oftetrahydrofuran. The reaction flask was cooled in an ice-bath. Withstirring at 0° C., cyclohexylmagnesium chloride (2.0 M in ether, 12.5mL, 25 mmol) was slowly added into the reaction flask. After beingstirred at 0° C. for 10 minutes, manganese chloride (0.5 M intetrahydrofuran, 60 mL, 30 mmol) was added to the reaction mixture,which was allowed to warm to room temperature over 20 minutes. Stirringwas discontinued and solids settled to the bottom of the reactionvessel. Without transferring the solids, the reaction solution wascannulated to a flask containing Ni(dppe)Cl₂ (0.04 g, 0.3 mol %) in 10mL of tetrahydrofuran at room temperature. The resulting mixture wasstirred at room temperature for 24 hours. A dark-purple precipitategradually formed over the course of the 24 hours. The entire mixture wasthen poured into 100 mL of methanol. The resulting dark precipitate wasfiltered, washed with methanol, and then dried under high vacuum.

Similar results were obtained as in Example 1, with the exception thatby employing 1.2 equivalents of MnCl₂, the regioregularity of the crudepolymer increased to about 92%.

Example 3 Comparative Example

Poly(3-hexylthiophene) was prepared by the method as substantiallydescribed in U.S. Pat. No. 6,166,172 for the preparation ofpoly(3-dodecylthiophene). A sample of 2,5-dibromo-3-hexylthiophene wasdissolved in tetrahydrofuran, methyl magnesium bromide (1.3 equivalent)was added, and the mixture was refluxed for six hours. The catalystNi(dppp)Cl₂ (1 mol %) was added and the solution was then refluxed fortwo hours. The crude poly(3-hexyl-thiophene) was isolated and was foundto possess 89% HT couplings, as determined by ¹H NMR analysis (analysisand integration of the C-4 vinyl proton and the C-3 α-methyleneprotons). The purification procedure of Example 1 of the '172 patent(Soxhlet extraction with three different organic solvents) was notconducted in order to provide a direct comparison with the crudepoly(3-hexylthiophene) prepared by the methods described herein.

As a comparison to the method described in the '172 patent,poly(3-hexylthiophene) was prepared by the method described in Example 1above with the following variations. Cyclohexylmagnesium chloride andMnCl₂ (1.5 equivalent each) were employed and the polymerization wascarried out starting at 0° C., and cooling bath was allowed to warm toroom temperature. As in Example 1, only 0.3 mol % of Ni(dppe)Cl₂catalyst was employed. The crude poly(3-hexylthiophene) was isolated andwas found to possess 92% HT couplings, as determined by ¹H NMR analysis.

By direct comparison of these two techniques, it was found thatemploying the manganese transmetallation technique afforded apoly(3-hexylthiophene) with an increased HT coupling of about 3%. Thisincreased HT purity results in less time, solvent, energy, and expenserequired to purify the product for use in the various devices describedherein.

Examples 4-39 Preparation of Regioregular HT Poly(3-hexylthiophene

A. Preparation of Thienylmanganese Chloride Reagents

To an oven-dried 250 mL round-bottomed flask was added 6.52 grams (20mmol) 2,5-dibromo-3-hexylthiophene and 40 mL of tetrahydrofuran. Theflask was cooled to 0° C. in an ice bath with stirring and 10 mL (20mmol) isopropylmagnesium chloride (2.0 M in tetrahydrofuran) was addedwith a syringe. The mixture was stirred at 0° C. for 5 minutes to affordthe thienyl-Grignard solution.

To another oven-dried 250 mL round-bottomed flask was added 2.8 grams(22 mmol) MnCl₂ and 40 mL of tetrahydrofuran and stirred at roomtemperature. To this was added via a cannula, the above thienyl-Grignardsolution to obtain a gold-colored mixture. The solution was stirred atroom temperature for twelve hours and allowed to settle overnight toafford a gold-colored liquid and a yellow precipitate (thethienylmanganese chloride reagent).

B. Preparation of Thienylmanganese Bromide Reagents

MnBr₂ was substituted for MnCl₂ in the above procedure to afford thethienylmanganese bromide reagent.

C. Polymerization of Organomanganese Reagents with the Reverse-AdditionProcedure (Addition of Ni(II) Catalyst into the OrganomanganeseSolution)

The thienylmanganese chloride prepared above was placed in an oven-dried250 ml round-bottomed flask and cooled to 0° C. in an ice-bath. To thiswas added 0.1 gram (0.1 mol %) Ni(dppe)Cl₂ in one portion with a powderaddition funnel. The mixture was stirred at 0° C. for 4-5 hours to forma polymer precipitate, warmed gradually to room temperature, and stirredat room temperature for an additional 19-20 hours. The mixture waspoured into 80 ml methanol and stirred for 20 minutes. The polymerprecipitate was filtered with a Buchner funnel, washed with methanol,and dried under a high vacuum to afford Examples 4-28 in Table 1.

Examples 29-36 in Table 2 were also prepared with this procedure bysubstituting thienylmanganese bromide for thienylmanganese chloride.

D. Polymerization of Organomanganese Reagents with the Standard AdditionProcedure (Addition of Organomanganese Solution into the Ni(II)Catalyst)

To a solution of 0.1 gram (0.1 mol %) Ni(dppe)Cl₂ in tetrahydrofuran wasadded the 0° C. solution of thienylmanganese chloride prepared above.The mixture was stirred at 0° C. for 4-5 hours to form a polymerprecipitate, warmed gradually to room temperature, and stirred at roomtemperature for an additional 19-20 hours. The mixture was poured into80 ml methanol and stirred for 20 minutes. The polymer precipitate wasfiltered with a Buchner funnel, washed with methanol, and dried under ahigh vacuum to afford Examples 29-31 in Table 3.

E. Purification of Poly(thiophene

A. Preparation of the L-grade poly(thiophene).

The crude polymer was placed in a Soxhlet thimble and extracted withhexanes for 24 hours. The polymer was dried under high vacuum to affordExamples 4, 6, 8, 10-11, 13, 16, and 19-20 in Table 1.

B. Preparation of the 4002 grade poly(thiophene).

The L-grade poly(thiophene) prepared above was placed in another Soxhletthimble and extracted with chloroform until the polymer was removed fromthe thimble. The solution was concentrated under reduced pressure untilpolymer was observed on the wall of the flask. The residue was pouredinto approximately double the volume of hexanes with stirring. Thepolymer was filtered with a Buchner funnel, washed with hexanes, anddried under a high vacuum to afford Examples 6, 10, 15, 17, and 23 inTable 1.

C. Preparation of the E-grade poly(thiophene).

The 4002 grade poly(thiophene) prepared above was placed in anotherSoxhlet thimble and extracted with chloroform until the polymer wasremoved from the thimble. The solution was concentrated under reducedpressure until polymer was observed on the wall of the flask. Theresidue was poured into methanol with stirring. The polymer was filteredwith a Buchner funnel, washed with methanol, and dried under a highvacuum to afford Examples 10, 15, and 22 in Table 1.

TABLE 1 Reverse-Addition Procedure using Thienylmanganese Chloride ¹HNMR Analysis Yield E- Example Conditions (%) Crude L-grade 4002 grade 40° C. for 6 hours 40 95:5 97:3 5 0° C. for 6 hours with 10% 39 TFT* 6 0°C. to 23° C. for 24 hours  94 (78)** 93:7 96:4 95:5 7 0° C. to 23° C.for 24 hours 82 8 0° C. to 23° C. for 24 hours 73 (60) 97:3 with 10% TFT9 0° C. to 23° C. for 24 hours 48 with @ 0.5 M 10 0° C. to 23° C. for 24hours 66 (57) 94:6 95:5 96:4 96:4 with @ 0.5 mol 11 23° C. for 24 hours64 82:18 94:6 12 23° C. for 24 hours 76 91:9 13 23° C. for 3 hours 7089:11 95:5*** 14 23° C. for 3 hours/q.w/aq- 61 92:8 95:5 and MeOHSolution 95:5*** 15 23° C. for 24 hours with 80 mmol 65 (60) 90:10 97:396:4 16 23° C. for 24 hours with 0.1 M 78 93:7 96:4 17 23° C. for 24hours with 0.1 83 (74) 94:6 M and 80 mmol 18 23-36° C. for 24 hours 7392:8 19 23° C. to reflux for 24 hours 82 92:8 95:5 20 23° C. for 24hours with  6 NMP 21 23° C. for 24 hours with 10 mol 73 (57  % TFT 2223° C. for 24 hours with 10% 91 (68) 95:5 TFT 23 23° C. for 24 hourswith 10% 65 (47) 92:8 93:7 94:6 TFT and 200 mmol 24 23° C. for 24 hoursat 0.05 mol 61 91:9 % Ni 25 Ni(PPh₃)₂Cl₂ n/a**** 26 Ni(PMe₃)₂Cl₂ n/a 27Fe(dppe)Cl₂ n/a 28 Co(dppe)Cl₂ n/a *TFT = α,α,α-trinitrofluorotoluene**= Soxholet Extraction ***= simple washing ****n/a = not available

TABLE 2 Reverse-Addition Procedure using Thienylmanganese Bromide ¹H NMRAnalysis Yield L- E- Example Conditions (%) Crude grade 4002 grade 29 0°C. for 6 hours 36 87:13 30 0 to 23° C. for 24 hours 56 90:10 96:4 31 23°C. for 24 hours 51 89:11 32 23° C. for 3 hours  70 (55)** 96:4 95:5 3323° C. for 24 hours and 200 mmol 55 (40) 93:7 93:7 94:6 34 23° C. for 24hours and 0.05 mmol 42 % Ni 35 23° C. for 24 hours and 10% 64 (40) 94:6TFT* 36 Reflux for 24 hours 55 (39) 94:6 *TFT =α,α,α-trinitrofluorotoluene **= Soxholet Extraction

TABLE 3 Standard Addition Procedure ¹H NMR Analysis Example ConditionsYield (%) Crude L-grade 4002 37 0 to 23° C. for 72 92:8 95:5 24 hours 3823° C. for 24 hours 78 92:8 39 23° C. to reflux for 63 85:15 87:13 24hours

The results in Tables 1-3 suggest that: a) a lower reaction temperatureaffords a higher regioregularity of the polymer (see, e.g., Table 1), b)the reverse addition procedure of Schemes 2-3 afford an easier work-upprocedure; c) the thienyl-Grignard reagent may be prepared at either 0°C. or at room temperature to afford a 80:20 ratio at 0° C., d) asuspension of manganese halide in tetrahydrofuran was used becausemanganese halide was not totally soluble in tetrahydrofuran at roomtemperature, e) no big advantage was observed using manganese bromideinstead of manganese chloride, f) the ratio of 5- and 2-thienylmanganesereagents was not a major factor in determining the regioregularity ofthe polymer, and g) the reverse addition procedure and lower reactiontemperature are the preferred conditions for polymerization.

Example 40 Exemplary poly(3-substituted-thiophenes)

Scheme 5 illustrates several of the polythiophenes that can be preparedby the methods described herein, wherein n is a value such that thepolythiophene polymer as a molecular weight of about 10,000 to about200,000; “Hex” is hexyl but can be any alkyl group as described herein;“Bn” is benzyl which can be optionally substituted as described herein;“Ar” is aryl as described herein; “Het” is heteroaryl or heterocyclyl asdescribed herein; m is 1 to about 20; and R is alkyl as describedherein.

All publications, patents, and patent documents are incorporated byreference herein, as though individually incorporated by reference. Theinvention has been described with reference to various specific andpreferred embodiments and techniques. However, it should be understoodthat many variations and modifications may be made while remainingwithin the spirit and scope of the invention.

1. A method of preparing regioregular HT poly(3-substituted-thiophene)comprising: a) contacting a 3-substituted-thiophene-metal complex with amanganese(II) halide to provide a 3-substituted-thiophene-manganesecomplex; and b) contacting the 3-substituted-thiophene-manganese complexwith a nickel(II) catalyst to provide the regioregular HTpoly(3-substituted-thiophene), wherein the 3-substituted-thiophene-metalcomplex is a 3-substituted-5-halo-thiophene metal complex, a3-substituted-2-halo-thiophene metal complex, or a mixture thereof. 2.The method of claim 1 wherein the 3-substituted-thiophene-metal complexis prepared by a method comprising contacting a2,5-dihalo-3-substituted-thiophene and an organometallic reagent toprovide the 3-substituted-thiophene-metal complex.
 3. The method ofclaim 2 wherein the organometallic reagent is a Grignard reagent, aGrignard-ate complex, an alkyl lithium reagent, an alkyl lithiumcuprate, an alkyl aluminum reagent, or an organozinc reagent.
 4. Themethod of claim 1 wherein the 3-substituted-thiophene-manganese complexis contacted with the nickel(II) catalyst at about −80° C. to about 35°C.
 5. The method of claim 1 wherein the3-substituted-thiophene-manganese complex is contacted with thenickel(II) catalyst at about −10° C. to about 30° C.
 6. The method ofclaim 1 wherein the 3-substituted-thiophene-manganese complex iscontacted with the nickel(II) catalyst at about 0° C. to about 27° C. 7.The method of claim 1 wherein the regioregularity of the regioregular HTpoly(3-substituted-thiophene) is greater than about 87%.
 8. The methodof claim 1 wherein the regioregularity of the regioregular HTpoly(3-substituted-thiophene) is greater than about 92%.
 9. The methodof claim 1 wherein the regioregularity of the regioregular HTpoly(3-substituted-thiophene) is greater than about 95%.
 10. The methodof claim 1 wherein the regioregular HT poly(3-substituted-thiophene) issubstituted with an alkyl, alkylthio, alkylsilyl, or alkoxy group thatis optionally substituted with one to about five ester, ketone, nitrile,amino, aryl, heteroaryl, or heterocyclyl groups, and the alkyl chain ofthe alkyl group is optionally interrupted by one to about ten O, S, orNH groups.
 11. The method of claim 1 wherein the regioregular HTpoly(3-substituted-thiophene) is substituted with a straight-chain,branched-chain, or cyclic (C₁-C₃₀)alkyl group.
 12. The method of claim 1wherein the regioregular HT poly(3-substituted-thiophene) is substitutedwith a straight-chain (C₁-C₁₂)alkyl group.
 13. The method of claim 1wherein the regioregular HT poly(3-substituted-thiophene) is substitutedwith a hexyl group.
 14. The method of claim 1 wherein the regioregularHT poly(3-substituted-thiophene) is substituted with a straight-chain,branched-chain, or cyclic (C₁-C₃₀)alkylthio group.
 15. The method ofclaim 1 wherein the regioregular HT poly(3-substituted-thiophene) issubstituted with a straight-chain (C₁-C₁₂)alkylthio group.
 16. Themethod of claim 1 wherein the regioregular HTpoly(3-substituted-thiophene) is substituted with a hexylthio group. 17.The method of claim 1 wherein the regioregular HTpoly(3-substituted-thiophene) is substituted with a straight-chain,branched-chain, or cyclic (C₁-C₃₀)alkoxy group.
 18. The method of claim1 wherein the regioregular HT poly(3-substituted-thiophene) issubstituted with a straight-chain (C₁-C₁₂)alkyloxy group.
 19. The methodof claim 1 wherein the regioregular HT poly(3-substituted-thiophene) issubstituted with a hexoxy group.
 20. The method of claim 1 whereinaverage weight molecular weight of the regioregular HTpoly(3-substituted-thiophene) is about 5,000 to about 200,000.
 21. Themethod of claim 1 wherein average weight molecular weight of theregioregular HT poly(3-substituted-thiophene) is about 40,000 to about60,000.
 22. The method of claim 1 wherein the regioregular HTpoly(3-substituted-thiophene) prepared has a polydispersity index ofabout 1 to about 2.5.
 23. The method of claim 1 wherein the regioregularHT poly(3-substituted-thiophene) prepared has a polydispersity index ofabout 1.2 to about 2.2.
 24. The method of claim 2 wherein the2,5-dihalo-3-substituted-thiophene is a2,5-dichloro-3-substituted-thiophene, a2,5-dibromo-3-substituted-thiophene, or a2,5-diiodo-3-substituted-thiophene.
 25. The method of claim 2 whereinthe 2,5-dihalo-3-substituted-thiophene is a2,5-dibromo-3-substituted-thiophene.
 26. The method of claim 2 whereinthe organometallic reagent is a Grignard reagent.
 27. The method ofclaim 26 wherein the Grignard reagent is a (C₁-C₃₀)alkyl magnesiumhalide or a (C₆-C₁₄)aryl magnesium halide.
 28. The method of claim 26wherein the Grignard reagent is a (C₅-C₆)alkyl magnesium halide or aphenyl magnesium halide.
 29. The method of claim 26 wherein the Grignardreagent is a cyclopentyl magnesium halide, a cyclohexyl magnesiumhalide, or a phenyl magnesium halide.
 30. The method of claim 26 whereinthe Grignard reagent is a magnesium fluoride, magnesium chloride, amagnesium bromide, or a magnesium iodide.
 31. The method of claim 26wherein the Grignard reagent is cyclopentyl magnesium chloride,cyclohexyl magnesium chloride, or phenyl magnesium chloride.
 32. Themethod of claim 2 wherein the organometallic reagent is an alkyl lithiumreagent or an aryl lithium reagent.
 33. The method of claim 32 whereinthe organometallic reagent is a (C₁-C₃₀)alkyl lithium or a (C₆-C₁₄)aryllithium.
 34. The method of claim 32 wherein the organometallic reagentis a (C₁-C₆)alkyl lithium or phenyl lithium.
 35. The method of claim 32wherein the organometallic reagent is methyl lithium, cyclohexyllithium, or phenyl lithium.
 36. The method of claim 1 wherein the amanganese(II) halide is manganese chloride, manganese bromide, manganeseiodide, or manganese fluoride.
 37. The method of claim 1 wherein the amanganese(II) halide is manganese chloride.
 38. The method of claim 1wherein the nickel(II) catalyst comprises phosphine ligands.
 39. Themethod of claim 1 wherein the nickel(II) catalyst comprises halideligands.
 40. The method of claim 1 wherein the nickel(II) catalyst is,or is derived from, Ni(dppe)Cl₂, Ni(dppp)Cl₂, Ni(PPh₃)₂Br₂,1,5-cyclooctadienebis(triphenyl) nickel, dichoro(2,2′-dipyridine)nickel, tetrakis(triphenylphosophine) nickel, NiO, NiF₂, NiCl₂, NiBr₂,NiI₂, NiAs, Ni(dmph)₂, BaNiS, or a combination thereof.
 41. The methodof claim 40 wherein the nickel(II) catalyst is Ni(dppe)Cl₂ orNi(dppp)Cl₂.
 42. The method of claim 1 wherein a sub-stoichiometricamount of nickel(II) catalyst is employed.
 43. The method of claim 1wherein about 0.01 mol % to about 100 mol % of nickel(II) catalyst isemployed.
 44. The method of claim 1 wherein about 0.1 mol % to about 5mol % of nickel(II) catalyst is employed.
 45. The method of claim 1wherein about 0.1 mol % to about 3 mol % of nickel(II) catalyst isemployed.
 46. The method of claim 1 wherein about 1 to about 2equivalents of the manganese(II) halide are employed, with respect tothe 3-substituted-thiophene-metal complex.
 47. The method of claim 1wherein about 1.0 to about 1.5 equivalents of the manganese(II) halideare employed, with respect to the 3-substituted-thiophene-metal complex.48. The method of claim 2 wherein about 1 to about 5 equivalents of theorganometallic reagent are employed, with respect to the2,5-dihalo-3-substituted-thiophene.
 49. A method of preparingpoly(thiophene) comprising: a) contacting a thiophene-metal complex witha manganese(II) halide to provide a thiophene-manganese complex; and b)contacting the thiophene-manganese complex with a nickel(II) catalyst toprovide the poly(thiophene), wherein the thiophene-metal complex is a5-halo-thiophene metal complex, a 2-halo-thiophene metal complex, or amixture thereof.
 50. A method of preparing poly(thiophene) comprising:a) contacting a 2,5-dihalo-thiophene and an organometallic reagent toprovide a thiophene-metal complex; b) contacting the thiophene-metalcomplex with a manganese(II) halide to provide a thiophene-manganesecomplex; and c) contacting the thiophene-manganese complex with anickel(II) catalyst to provide the poly(thiophene).
 51. The method ofclaim 50 wherein the organometallic reagent is a Grignard reagent, aGrignard-ate complex, an alkyl lithium reagent, an alkyl lithiumcuprate, an alkyl aluminum reagent, or an organozinc reagent.
 52. Amethod of preparing poly(3,4-disubstituted-thiophene) comprising: a)contacting a 3,4-disubstituted-thiophene-metal complex with amanganese(II) halide to provide a 3,4-disubstituted-thiophene-manganesecomplex; and b) contacting the 3,4-disubstituted-thiophene-manganesecomplex with a nickel(II) catalyst to provide thepoly(3,4-disubstituted-thiophene), wherein the3,4-disubstituted-thiophene-metal complex is a3,4-disubstituted-5-halo-thiophene metal complex, a3,4-disubstituted-2-halo-thiophene metal complex or a mixture thereof.53. A method of preparing poly(3,4-disubstituted-thiophene) comprising:a) contacting a 2,5-dihalo-3,4-substituted-thiophene and organometallicreagent to provide a 3,4-disubstituted-thiophene-metal complex; b)contacting the 3,4-disubstituted-thiophene-metal complex with amanganese(II) halide to provide a 3,4-disubstituted-thiophene-manganesecomplex; and c) contacting the 3,4-disubstituted-thiophene-manganesecomplex with a nickel(II) catalyst to provide thepoly(3,4-disubstituted-thiophene).
 54. The method of claim 53 whereinthe organometallic reagent is a Grignard reagent, a Grignard-atecomplex, an alkyl lithium reagent, an alkyl lithium cuprate, an alkylaluminum reagent, or an organozinc reagent.
 55. The method of claim 52wherein the substituents of the poly(3,4-substituted-thiophene) are thesame.
 56. The method of claim 52 wherein the substituents of thepoly(3,4-substituted-thiophene) are not the same.
 57. The method ofclaim 52 wherein the poly(3,4-substituted-thiophene) monomers arearranged in a substantially HT orientation.
 58. A regioregular HTpoly(3-substituted-thiophene) prepared by a method comprising: a)contacting a 2,5-dihalo-3-substituted-thiophene and a Grignard reagentto provide a 3-substituted-thiophene-magnesium complex; b) contactingthe 3-substituted-thiophene-magnesium complex with a manganese(II)halide to provide a 3-substituted-thiophene-manganese complex; and c)contacting the 3-substituted-thiophene-manganese complex with anickel(II) catalyst to provide the regioregular HTpoly(3-substituted-thiophene).
 59. An electronic device comprising acircuit constructed with the regioregular HT polythiophene prepared bythe method of claim
 1. 60. The electronic device of claim 59 wherein thedevice is an RFID tag, a plastic photovoltaic device, a plastic lightingdevice, or an OLED.
 61. A regioregular HT poly(3-substituted-thiophene)prepared by claim
 1. 62. The regioregular HTpoly(3-substituted-thiophene) of claim 61 wherein the crude regioregularHT poly(3-substituted-thiophene) has a regioregularity of at least about87%.
 63. The regioregular HT poly(3-substituted-thiophene) of claim 62wherein the crude regioregular HT poly(3-substituted-thiophene) has aregioregularity of at least about 92%.
 64. The regioregular HTpoly(3-substituted-thiophene) of claim 63 wherein the crude regioregularHT poly(3-substituted-thiophene) has a regioregularity of at least about87%.
 65. The regioregular HT poly(3-substituted-thiophene) of claim 61in the form of a thin film.
 66. A conductive polymer comprising HTpoly(3-substituted-thiophene) having at least about 92% regioregularity;an average weight molecular weight of about 30,000 to about 70,000; anda conductance of about 10⁻⁵ to about 10⁻⁶ seimens/cm.
 67. The conductivepolymer of claim 66 wherein the substituent of the HTpoly(3-substituted-thiophene) is an organic or inorganic group.
 68. Theconductive polymer of claim 67 wherein the substituent of the HTpoly(3-substituted-thiophene) is an alkyl, alkylthio, alkylsilyl, oralkoxy group that is optionally substituted with one to about fiveester, ketone, nitrile, amino, aryl, heteroaryl, or heterocyclyl groups,and the alkyl chain of the alkyl group is optionally interrupted by oneto about ten O, S, or NH groups.
 69. The method of claim 1 wherein the3-substituted-thiophene-manganese complex is added to the nickel(II)catalyst.
 70. The method of claim 1 wherein the nickel(II) catalyst isadded to the 3-substituted-thiophene-manganese complex.
 71. Theregioregular HT poly(3-substituted-thiophene) of claim 58 wherein the3-substituted-thiophene-manganese complex is added to the nickel(II)catalyst.
 72. The regioregular HT poly(3-substituted-thiophene) of claim58 wherein the nickel(II) catalyst is added to the3-substituted-thiophene-manganese complex.